JPS59170066A - Manufacture of 3,5,6-trichloro-1h-pyridin-2-one - Google Patents
Manufacture of 3,5,6-trichloro-1h-pyridin-2-oneInfo
- Publication number
- JPS59170066A JPS59170066A JP59045741A JP4574184A JPS59170066A JP S59170066 A JPS59170066 A JP S59170066A JP 59045741 A JP59045741 A JP 59045741A JP 4574184 A JP4574184 A JP 4574184A JP S59170066 A JPS59170066 A JP S59170066A
- Authority
- JP
- Japan
- Prior art keywords
- pyridin
- reaction
- chloro
- chlorine
- solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- WCYYAQFQZQEUEN-UHFFFAOYSA-N 3,5,6-trichloropyridine-2-one Chemical compound ClC=1C=C(Cl)C(=O)NC=1Cl WCYYAQFQZQEUEN-UHFFFAOYSA-N 0.000 title 1
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 239000000243 solution Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 10
- 239000000460 chlorine Substances 0.000 claims description 10
- 229910052801 chlorine Inorganic materials 0.000 claims description 10
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims description 7
- 238000005660 chlorination reaction Methods 0.000 claims description 7
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 6
- 239000011541 reaction mixture Substances 0.000 claims description 6
- CLNNBQDAAGDAHI-UHFFFAOYSA-N 6-chloro-1h-pyridin-2-one Chemical compound OC1=CC=CC(Cl)=N1 CLNNBQDAAGDAHI-UHFFFAOYSA-N 0.000 claims description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 5
- VTLCZUQBQIUEQA-UHFFFAOYSA-N 1,3-dichloropyridin-2-one Chemical compound ClC1=CC=CN(Cl)C1=O VTLCZUQBQIUEQA-UHFFFAOYSA-N 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 238000003379 elimination reaction Methods 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims 1
- 230000008030 elimination Effects 0.000 claims 1
- 239000007789 gas Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 229910052785 arsenic Inorganic materials 0.000 description 2
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- ULDHMXUKGWMISQ-UHFFFAOYSA-N carvone Chemical compound CC(=C)C1CC=C(C)C(=O)C1 ULDHMXUKGWMISQ-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- UBQKCCHYAOITMY-UHFFFAOYSA-N pyridin-2-ol Chemical compound OC1=CC=CC=N1 UBQKCCHYAOITMY-UHFFFAOYSA-N 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- PPKPKFIWDXDAGC-IHWYPQMZSA-N (z)-1,2-dichloroprop-1-ene Chemical compound C\C(Cl)=C\Cl PPKPKFIWDXDAGC-IHWYPQMZSA-N 0.000 description 1
- QWVOLCQYBXARGY-UHFFFAOYSA-N 1-chloropyridin-2-one Chemical compound ClN1C=CC=CC1=O QWVOLCQYBXARGY-UHFFFAOYSA-N 0.000 description 1
- WLAMNBDJUVNPJU-UHFFFAOYSA-N 2-methylbutyric acid Chemical compound CCC(C)C(O)=O WLAMNBDJUVNPJU-UHFFFAOYSA-N 0.000 description 1
- 239000005973 Carvone Substances 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical compound CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- RMIODHQZRUFFFF-UHFFFAOYSA-N methoxyacetic acid Chemical compound COCC(O)=O RMIODHQZRUFFFF-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 150000004965 peroxy acids Chemical class 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 239000012258 stirred mixture Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- PVFOMCVHYWHZJE-UHFFFAOYSA-N trichloroacetyl chloride Chemical compound ClC(=O)C(Cl)(Cl)Cl PVFOMCVHYWHZJE-UHFFFAOYSA-N 0.000 description 1
- 235000019583 umami taste Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/62—Oxygen or sulfur atoms
- C07D213/63—One oxygen atom
- C07D213/64—One oxygen atom attached in position 2 or 6
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Pyridine Compounds (AREA)
Abstract
(57)【要約】本公報は電子出願前の出願データであるた
め要約のデータは記録されません。(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.
Description
【発明の詳細な説明】
本発明は、ろ、 ５ 、６−１−リクロルーｉＨ−ピリ
ジンー２−オンの新規製法に関する。この化合物は、殺
虫剤の合成の際の重要な中間生成物である。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a new process for the preparation of 5,6-1-lichloro-iH-pyridin-2-one. This compound is an important intermediate in the synthesis of pesticides.
この化合物の合成法としては、６−ブロム−２−エトギ
シピリジンの塩素比および引続（６−フロム−３，５−
シクロルー２−エトキシ−ピリジンの分離および）・ロ
デン交換ならびに６−クロル−１Ｈ−ピリジン−２−オ
ンの塩素化が知られている（ ａｅｎ Ｈｅｒｔｏｇ
、 Ｄｅ Ｂｒｕｙｎ ：Ｒｅｃｅｕｉｌ ７０ （
１９５１）、 １８２〜１９０）。双方の塩素化反応は
含水過酸ｆヒ水素および含水塩酸を用（゛・で行なわれ
る。こｉｔは記載されたように、たんに小さな実験室用
バッチ中で最１１のダラム量を用いて効果的に実施し５
ろにすぎない。より大きな量では、制御不能な副反Ｌ６
、が進行し、所望生成物の収率を著しく低下する。The synthesis method for this compound includes the chlorine ratio of 6-bromo-2-ethogycypyridine and the subsequent (6-from-3,5-
Separation of cyclo-2-ethoxy-pyridine and )-lodene exchange and chlorination of 6-chloro-1H-pyridin-2-one are known (aen Hertog
, De Bruyn:Receuil 70 (
1951), 182-190). Both chlorination reactions are carried out using aqueous peracid f arsenic and aqueous hydrochloric acid. This is done using up to 11 duram quantities in just small laboratory batches, as described. Effective implementation5
It's just a ro. At larger quantities, uncontrollable vice-reaction L6
, which significantly reduces the yield of the desired product.
３ 、４ 、６− ）リクロルー１Ｈ〜ピリジンー２−
オンの経済的な手工業的製造はこの方法では不可能であ
る。3,4,6-) Lichlor-1H~Pyridine-2-
Economical manual production of on is not possible with this method.
ヨーロッパ゛特許第θ口３１］２１４Ａ号明４１＋１
ｊｌから、塩化トリクロルアセチル２よびアセトニトリ
ルかｊらの直接合成は公知である。この場ｆ：ン、この
反応が高毒性出発物質化用い費用（））か９・る加圧反
応で行なわれる事を別にしても、ツタｒ望の３．５．６
〜トリクロル−１Ｈ−ピリジン−２−オンも２，３，５
．６−チトラークロルビリジンも生じるので、この双方
の近縁物質をさらに苦労して互いに分離しなげればなら
ない。European Patent No. θ Port 31] 214A No. 41+1
The direct synthesis of trichloroacetyl chloride 2 and acetonitrile from jl is known. In this case, apart from the fact that this reaction is carried out in a pressurized reaction using a highly toxic starting material ()), it is important to note that
~Trichlor-1H-pyridin-2-one is also 2,3,5
．． Since 6-thitrachlorpyridine is also formed, these two closely related substances have to be separated from each other even more laboriously.
従って、本発明の評題は、３，５．６−１−ＩＪジクロ
ル１Ｈ−ピリジン−２−オンを製造する冬め・、Ｈ，ｖ
）化合物が容易“入手しうる出発物質からできるかきり
簡単な工程で良好な収率および純度で、大工業的バッチ
でも経尚的に製造する小のでさる方法を提供１−る事で
ある。Therefore, the subject of the present invention is to produce 3,5.6-1-IJ dichlor 1H-pyridin-2-one in winter.
The object of the present invention is to provide a small-scale process in which the compounds can be easily prepared from readily available starting materials, in a simple process, with good yields and purity, even in large industrial batches.
課題の解決は、特許請求の範囲第１項〜第５項による方
法により行なわれる。The problem is solved by the method according to claims 1 to 5.
３ 、５ 、６−１−ジクロル−１Ｈ−ピリジンー２−
オンの経済的に最も簡単な製造は、容易にイ！Ｉら−Ｊ
ｚる６−クロル−１Ｈ−ビ′リジンー２〜オノと塩素と
の直接反応である。残念ながら、こ７ｔは今まで、成果
を収めず、そｉｔゆえデンーヘルトソポおよびデ・グリ
ュノも過辰１ｅ 、／Ｊ（索ｄよび塩１ヒ水素を用いる
間ｊ妾塩素ｒヒ廻よる方法をとった。3,5,6-1-dichloro-1H-pyridine-2-
The economically simplest manufacture of on-line is easy! I et al-J
This is a direct reaction between 6-chloro-1H-bi'lysine-2-ono and chlorine. Unfortunately, this method has so far not yielded any results, which is why Dengeltsopo and De Gruno have also adopted the method of circulating chlorine while using salt and arsenic. Ta.
６−／コル−１Ｈ−ヒｊＪ ７ンー２−オンノ浴液中へ
塩素ガスを尋人する際には極ψＩＭな発熱反応が行なわ
れ、その、結果として制御不能な分解反応が進行する。When chlorine gas is introduced into the bath solution, an extremely exothermic reaction takes place, resulting in an uncontrollable decomposition reaction.
この所望でない反応は、反応体を低いａ度で互いに作用
させ、たとえは６−クロ／Ｌ／−ＩＨ−ピリジン−２−
オンの希、ラム中へ担持ガスで希釈された塩素を６大す
る事によっても抑圧できない。This undesired reaction forces the reactants to interact with each other at low a degrees, such as 6-chloro/L/-IH-pyridine-2-
Even if chlorine is diluted with a carrier gas and added to the ram, it cannot be suppressed.
しかし驚いた事に、塩素ガスをカルボン酸水溶液中の６
−クロル−１Ｈ−ピリジン−２−オンの溶液に導通し、
温度を１５〜３０’Ｃの範囲に保つ場合、３，５．６−
）ジクロル−１Ｈ−ピリジンー２−オンへの６−クロル
−１Ｈ−ピリジン−２−オンの慎重かつ選択的塩素［ヒ
に成功する。ガス空間から溶液により吸収される塩素量
および塩素分配は、所望の楡素化反応の・１〕１重であ
るにも拘らす経済的な実施を可能にする反応の出発生成
物は、純粋ならびに工業用の６−クロル−１Ｈ−ピリジ
ン−２−オンであってもよ℃・０本発明による方法のも
う１つの簡単な実施形では直接、容易に入手出来る２−
クロル−６−メドキンピリジンから６−クロル−１Ｈ−
ピリジン−２−オンを製造する際に生しる反応混合物が
、反応生成物をあらかじめ分離せずに得られる。このた
めに、２−クロル−６−メドキシビリジンから成る懸濁
液を１００’Ｃに加熱し、少量ずつ嬢塩酸約２倍モル腋
をカｌえ、その場合反応混合物を還流下に保つ。この酸
添加は約２〜４時間かかる。それに、混合物の沸１１！
？ 旨度での１５〜２０時間の後反応が続く。このエー
テル離脱反応の開基化メチルが逃出し、このものは純粋
な形で捕集し、他の合成に使用する事ができる。残留す
る反応混合物は塩素化反応の出発生成物として使用する
。これに熱時に液状カルボン酸またはカルボン散水溶液
を加え、１５〜ろＤ ０Ｃに冷却する。However, to my surprise, chlorine gas was
- into a solution of chloro-1H-pyridin-2-one;
If the temperature is kept in the range 15-30'C, 3,5.6-
) Successful careful and selective chlorination of 6-chloro-1H-pyridin-2-one to dichloro-1H-pyridin-2-one. The amount of chlorine absorbed by the solution from the gas space and the chlorine distribution are 1) of the desired hydrogenation reaction.Although the starting products of the reaction are pure and 6-Chlor-1H-pyridin-2-one may also be used. Another simple embodiment of the process according to the invention may be directly available 6-chloro-1H-pyridin-2-one.
Chlor-6-medquinpyridine to 6-chloro-1H-
The reaction mixture resulting from the preparation of pyridin-2-one is obtained without prior separation of the reaction products. For this, a suspension consisting of 2-chloro-6-medoxyviridine is heated to 100 DEG C. and about twice the molar amount of hydrochloric acid is dissolved in portions, the reaction mixture being kept under reflux. This acid addition takes approximately 2-4 hours. Besides, boil the mixture 11 times!
? After 15 to 20 hours of umami, the reaction continues. The opening methyl of this ether elimination reaction escapes and can be collected in pure form and used in other syntheses. The remaining reaction mixture is used as starting product for the chlorination reaction. A liquid carboxylic acid or carvone aqueous solution is added to the mixture while it is hot, and the mixture is cooled to 15°C to 0°C.
塩素化反応の際純粋な６−クロル−１Ｈ−ピリジン−２
−オンから出発すると、この物質を６０〜７０％のカル
ボン酸水溶液に溶解する。During the chlorination reaction pure 6-chloro-1H-pyridine-2
Starting from -one, this material is dissolved in a 60-70% aqueous carboxylic acid solution.
カルボン酸の量は、６−クロル−１Ｈ−ピリジン−２−
オンを反応温度で溶液中に保つの足十分であるべきであ
る。The amount of carboxylic acid is 6-chloro-1H-pyridine-2-
It should be sufficient to keep the solution in solution at the reaction temperature.
カルボン酸としては、反応６情度で、即ぢ１５〜６０°
Ｇの範囲内で塩素に対して不活性であり、この温度で液
状であるようなもの、たとえば酢酸、ゾロピオン酸、酪
酸または吉草酸が使用されるが、アルギル基が置換また
は分枝されているようなもの、たとえばメトキシ酢酸、
ジメチル酢酸、メチル−エチル酢酸またはイノ吉草酸も
使用される。As a carboxylic acid, the reaction temperature is 15 to 60°.
Those which are inert toward chlorine within the range of such as methoxyacetic acid,
Dimethylacetic acid, methyl-ethylacetic acid or inovaleric acid are also used.
塩素化反応は、か（はん機および少なくとも２つの閉鎖
可能な開口を備え、該開口を通ってガスを溶液上に存在
するガス空間中へ導入および場合により排出しうる密閉
容器中で行／、ｌ：われる。反応容器は付加的に答易な
試料取り出しが可能であるべきである。溶液を冷却下に
か（はんし、この溶液に塩素ガスを導通し、その１易合
ガス空間は有利に約５０〜２００ミリバールの軽度の過
圧下にある。塩素供給は、反応温度が前述の範囲を上廻
らないように定められていなければならない。これは約
５〜１０時間かかる。反応の間、形成した３ 、 ５
、６− ） ＩＪクロ／レ−１Ｈ−ピリジン−２−オン
は沈殿し、従って懸濁液が形成する。The chlorination reaction is carried out in a closed container equipped with a burner and at least two closable openings through which gas can be introduced and optionally discharged into the gas space present above the solution. The reaction vessel should additionally allow for easy sample removal.The solution should be cooled and chlorine gas passed through it, and the gas space is preferably under a slight overpressure of approximately 50 to 200 mbar.The chlorine feed must be such that the reaction temperature does not exceed the aforementioned range.This takes approximately 5 to 10 hours. Between 3 and 5
, 6-) IJ clo/re-1H-pyridin-2-one precipitates, thus forming a suspension.
反応の終了後、過剰の塩素ガスを少量の亜硫酸ナトリウ
ムの添加により除去する。それにより、反応混合物の中
和後に濾別、洗浄および乾燥されろ最終生成物の改良さ
れた色安定性が肖られろ。After the end of the reaction, excess chlorine gas is removed by adding a small amount of sodium sulfite. Thereby, improved color stability of the final product, which is filtered off, washed and dried after neutralization of the reaction mixture, is observed.
例・
１０１の三頚フラスコ中で、２−クロル−６−メドキソ
ビリジン８６１．！？（６モル）および水１００１１＋
１１！から成る１ｏｏ０ｃに加熱され、よ（かくはんさ
れた混合物に、２．５時間のうちに化学用ボ［を度の濃
ｉＭ畝１１６７＆（１２モル）を均一に滴加する。引、
読き、還流温度で１６時間の後反応時間を行なう。その
後、６０％の酢酸溶液５０００ Ｉｎｉを添加し、引続
き軽度の過圧（１００ミ！Ｊバール）下に７時間、塩素
ガス９８０ｇを溶液上のガス空間中へ導入し、その場合
冷却により反応混合物の温度は２０〜２２℃に保つ。塩
素添加の終了後、亜硫酸水素ナトリウム２０ｇを添加す
る。懸濁液をさらに１５分か（はんする。その後、２０
〜６０℃で５０％力性ノーダ溶液１１２０．９を滴加し
、引続き生成物を吸引濾過し、濾液が中性になるまで水
で洗浄する。１００℃で乾燥した目的物は１７５°Ｃ（
文献１７４〜１７５°Ｃ）の融点を有する、収量：１ｉ
ｏｏ、ｙ−理論値の９６％。Example - In a three-necked flask of 101, 2-chloro-6-medoxoviridine 861. ! ? (6 mol) and water 10011+
11! To the stirred mixture, heated to 100C and consisting of 100C, 12 moles of chemical solution (12 moles) of a chemical concentration of 1167% is uniformly added dropwise over a period of 2.5 hours.
A post-reaction time of 16 hours is carried out at reflux temperature. Thereafter, 5000 Ini of a 60% strength acetic acid solution is added and subsequently 980 g of chlorine gas are introduced into the gas space above the solution under mild overpressure (100 m!J bar) for 7 hours, the reaction mixture being cooled. The temperature is maintained at 20-22°C. After the chlorine addition is complete, 20 g of sodium bisulfite are added. Leave the suspension for another 15 minutes, then 20 minutes.
At ~60 DEG C., 50% strength Noda solution 1120.9 is added dropwise and the product is subsequently filtered off with suction and washed with water until the filtrate is neutral. The object dried at 100°C is heated to 175°C (
Yield: 1i, with a melting point of 174-175 °C)
oo,y - 96% of theoretical value.
−必−Required
Claims (1)
．６−）ジクロル−１Ｈ−ピリジンー２−オンを製造す
る方法において、６−り゛ロルー１Ｈ−ピリジンー２−
オンを室温で液状であり、塩素ガスに対して不活性であ
るカルボン酸のカルボン酸水溶液に溶解し、反応容器中
で、塩素ガスを溶液上に存在するガス空間中へ導入する
事によって塩素化し、その場合反応温度を冷却により１
５−”３０°Ｃの範囲に保つ事を特徴とする、３，５．
６−ドリクロルー１Ｈ−ピリジン−２−オンの製法。 ２、 反応温度を２０〜２５°Ｃに保つ、特許請求の範
囲第１項記載の方法。 ６、 ガス空間が５０〜２０［］ミリバールの軽度の過
圧下にある、特許請求の範囲第１項または第２項記載の
方法。 ４、 塩素化を２−クロル−６−メドキシピリジンのエ
ーテル離脱直後に、６−クロル−１Ｈ−ピリジン−２−
オンを単離せずに行なう、特許請求の範囲第１項〜第６
項のいずれか１項記載の方法。 ５、 エーテル離脱後、カルボン酸をまだ温かい反応混
合物に添加する、特許請求の範囲第４項記載の方法。1.6-chloro-1H-pyridin-2-one to 3.5
．． 6-) In the method for producing dichloro-1H-pyridin-2-one, 6-dichloro-1H-pyridin-2-one
chlorine is dissolved in an aqueous solution of a carboxylic acid that is liquid at room temperature and inert to chlorine gas, and chlorinated in a reaction vessel by introducing chlorine gas into the gas space present above the solution. , in which case the reaction temperature is reduced to 1 by cooling.
5-" 3,5. characterized by being maintained within a range of 30°C.
Method for producing 6-dolychloro-1H-pyridin-2-one. 2. The method according to claim 1, wherein the reaction temperature is maintained at 20 to 25°C. 6. The method according to claim 1 or 2, wherein the gas space is under a slight overpressure of 50 to 20 mbar. 4. Chlorination was carried out immediately after the ether removal of 2-chloro-6-medoxypyridine, and 6-chloro-1H-pyridine-2-
Claims 1 to 6, which are carried out without isolating the on.
The method described in any one of paragraphs. 5. Process according to claim 4, in which the carboxylic acid is added to the still warm reaction mixture after ether elimination.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19833308800 DE3308800A1 (en) | 1983-03-12 | 1983-03-12 | METHOD FOR PRODUCING 3,5,6-TRICHLOR-1H-PYRIDIN-2-ON |
| DE33088004 | 1983-03-12 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS59170066A true JPS59170066A (en) | 1984-09-26 |
Family
ID=6193251
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59045741A Pending JPS59170066A (en) | 1983-03-12 | 1984-03-12 | Manufacture of 3,5,6-trichloro-1h-pyridin-2-one |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US4546190A (en) |
| EP (1) | EP0124657B1 (en) |
| JP (1) | JPS59170066A (en) |
| DE (2) | DE3308800A1 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101885702B (en) * | 2010-07-21 | 2011-11-09 | 青州市至诚化工有限公司 | Method for synthesizing 3,5,6-trichloropyridin 2 ol sodium by liquid-phase normal-pressure buffer solution method |
| CN101880258B (en) * | 2010-07-21 | 2011-12-07 | 青州市至诚化工有限公司 | Method for synthesizing 3, 5, 6-trichloropyridine natrium phenolicum by liquid-phase normal-pressure organic solvent method |
| CN101899000B (en) * | 2010-07-21 | 2011-11-09 | 青州市至诚化工有限公司 | Method for synthesizing 3,5,6-trichloropyridine phenol sodium by liquid phase normal pressure direct catalytic chlorination |
| CN102643227A (en) * | 2011-02-16 | 2012-08-22 | 山东谦诚工贸科技有限公司 | Method for synthesizing 3,5,6-trichloro-2-pyridol by chlorination of 6-chloro-2-hydroxypyridine sodium salt |
| CN102643226A (en) * | 2011-02-16 | 2012-08-22 | 山东谦诚工贸科技有限公司 | Method for synthesizing 3,5,6-trichloro-2-pyridol by chlorination of 6-chloro-2-hydroxypyridine sodium salt |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2951844A (en) * | 1958-11-05 | 1960-09-06 | Olin Mathieson | Cyclic process for manufacture of 2-chloropyridine-1-oxide |
| US3357984A (en) * | 1965-07-20 | 1967-12-12 | Olin Mathieson | Preparation of tetrachloro-and pentachloropyridine-1-oxides |
| US3682938A (en) * | 1970-12-18 | 1972-08-08 | Dow Chemical Co | Bis(trifluoro methyl)-2-pyridinols |
| JPS55124763A (en) * | 1979-03-19 | 1980-09-26 | Ishihara Sangyo Kaisha Ltd | 5-trifluoromethyl-2-pyridone derivative |
-
1983
- 1983-03-12 DE DE19833308800 patent/DE3308800A1/en not_active Withdrawn
- 1983-12-14 EP EP83201773A patent/EP0124657B1/en not_active Expired
- 1983-12-14 DE DE8383201773T patent/DE3370154D1/en not_active Expired
-
1984
- 1984-02-27 US US06/583,910 patent/US4546190A/en not_active Expired - Fee Related
- 1984-03-12 JP JP59045741A patent/JPS59170066A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| DE3370154D1 (en) | 1987-04-16 |
| EP0124657A1 (en) | 1984-11-14 |
| EP0124657B1 (en) | 1987-03-11 |
| US4546190A (en) | 1985-10-08 |
| DE3308800A1 (en) | 1984-09-13 |
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